Experiment No.: To Determine the Velocity Constant for the Hydrolysis of Methylacetate Using an Acid as Catalyst at Laboratory Temperature. Requirement: Methylacetate, N/2 HCl solution, N/15 NaOH solution, Phenolphthalein (indicator), Ice cold water, 2ml pipette, Conical flask, Conical flask with stopper (Erlenmeyer flask), 50ml measuring cylinder, 150ml & 250ml beaker. Theory: Methylacetate hydrolyses in presence of an acid (acts as catalyst) and produces acetic acid and methyl alcohol. CH3COOCH3 + H2O H+ CH3COOH + CH3OH Velocity of the reaction, v dx k ' CH 3 COOCH 3 H 2 O dt k CH 3COOCH3 where, k k ' H 2 O (Note: water is present in large excess, water concentration practically remain constant throughout the reaction.) In the above equation rate of reaction is determined by the first power of the concentration (of ester). Hence, the reaction is called first order reaction. It is also known as pseudounimolecular reaction. Let, a = initial concentration of ester (at t = 0) of the above reaction. (a-x) = Concentration of ester remaining at time t. The rate is represented by dx v k a x dt 2.303 a On integration, k log t ( a x) This reaction was followed by quenching an aliquot of the reaction mixture at different time and titrating the total acid (both acetic acid formed and the N/2 HCl acid taken originally) by a standard solution of N/15 NaOH. If V0, Vt and V are the volumes of N/15 NaOH consumed to neutralize the acids of a given volume of the reaction mixture at the beginning (t = 0), at time t, and at the end ( t = ) of the reaction respectively, the rate constant of the reaction can be expressed as k V V0 2.303 log t V Vt ---(1) where V0= titration reading at time t=0, at time t, and at t = . Prepared by Dr. S. Saha, Chemistry, BHU 1 because V V0 is proportional to the concentration of the total acetic acid formed or the conc. of ester in the beginning of the reaction, a and V Vt is proportional to the concentration of the unreacted ester (a-x) at time t. The equation 1 can be rearranged as follows log V V0 k t V Vt 2.303 [Note the similarity with y = mx + c (=0)] The velocity constant was determined from the slope (m = k ) of the graph of 2.303 V V0 vs t as well as directly using the equation 1 at each time. V Vt [An example of the graph was given at the end of this note.] log Procedure: N/15 NaOH solution was taken in the burette while 50ml N/2 HCl solution was taken in a stoppered conical flask using a measuring cylinder. 2ml methylacetate was pipetted out and poured into the conical flask and was shaked well. As soon as the ester was poured, the time count starts. 2ml of the reaction mixture was pipetted out immediately and was added to 25 ml of ice cold water in a conical flask (i.e., quenching of the reaction). 2-3 drops of phenolphthalein indicator was added in that quenched solution and was titrated against N/15 NaOH solution. Titration was completed as soon as possible. The burette reading, so obtained, was considered as V0 (since t = 0 min, assumed). When the stopwatch was seen to be at 5 min, again 2 ml of the reaction mixture was quenched and the titration was done following the same procedure. The burette reading so obtained was considered as V5 (since t = 5 min). The same procedure was repeated at t = 10, 20, 30, and 40 min to get the corresponding burette readings of V10, V20, V30, and V40 respectively [Note: Dany other convenient time gap may be used]. Finally, the reaction mixture was heated at 60-80o C for 20min (caution: Do not boil the solution. Do not stoppered the conical tightly, use a paper strip to avoid stuck). It was cooled down to room temperature. 2ml of this mixture was taken out in the conical and was titrated against the N/15 NaOH as described earlier. The reading was noted as V. Prepared by Dr. S. Saha, Chemistry, BHU 2 Observation and Calculation: Lab. Temperature: V0 = ml V = ml ml V V0 = o C Table. Burette reading at different times and corresponding calculated velocity constants. Sl. no. Time/ min 1. 2. 3. 4. 5. 5 10 20 30 40 Burette reading V Vt V V0 V Vt log V V0 V Vt k V V0 2.303 min-1 log t V Vt From the Table : k avg = From the Graph : k Graph = slope x 2.303 min-1 Result: Velocity constant for the hydrolysis of the methylacetate at laboratory temperature ( oC) was found to be: i) From table, k avg = min-1 min-1 ii) From Graph, k Graph = Experiment No.: To determine the velocity constant and half-life for the hydrolysis of methylacetate acid as catalyst at laboratory temperature. At t= t/2 (i.e., half life period: half of the reactant converted to the product) x= a/2 k 2.303 a 2.303 log log t ( a x) t1 2 t 1 0.693 2 a a a 2 2.303 log 2 t1 2 0.693 min 1 k Prepared by Dr. S. Saha, Chemistry, BHU 3 Example Graph 1: 0.20 0.18 0.16 log [(V-V0)/(V-Vt)] 0.14 0.12 0.10 0.08 0.06 0.04 Slope=0.00495 -2 -1 k = 1.14 x 10 min 0.02 0.00 0 5 10 15 20 25 30 35 40 45 t / min Prepared by Dr. S. Saha, Chemistry, BHU 4 Student 3: vinf V0sep 28 V0inst v 16 16.2 t vinf-vt 16.5 17.5 18.3 19.8 20.2 5 10 20 30 40 vinf-vos 11.5 10.5 9.7 8.2 7.8 vinf-v0ins log-sep log-ins 12 11.8 0.018483 0.011184 0.057992 0.050693 0.09241 0.08511 0.165367 0.158068 0.187087 0.179787 0.20 0.20 V0 from reaction mixture 0.18 V0 separately determined 0.18 0.16 0.16 0.14 log [(V-V0)/(V-V0)] log [(V-V0)/(V-V0)] 0.14 0.12 0.10 0.08 Slope=0.00464 -2 -1 k= 1.08x10 min 0.06 0.04 0.02 0.12 0.10 0.08 Slope=0.00495 -2 -1 k= 1.14x10 min 0.06 0.04 0.02 0.00 0 5 10 15 20 25 30 35 t/min Prepared by Dr. S. Saha, Chemistry, BHU 40 45 0.00 0 5 10 15 20 25 30 t/min 5 35 40 45